Shimadzu Corporation

Kazuma Maeda

Daisuke Okumura

Yoshikatsu Umemura

Tomoyuki Oshiro

Toshiya Matsubara

Shingo Fujioka

A chromatograph mass spectrometer according to an aspect of the present invention is a chromatograph mass spectrometer including: a chromatograph unit (LC unit) configured to separate components in a sample; and a mass spectrometer (MS unit) configured to execute mass spectrometry on ions having a specific mass-to-charge ratio derived from a compound for each compound temporally separated by the chromatograph unit, the chromatograph mass spectrometer further including: an analysis condition setting unit () configured to allow a user to input a width of a peak on a chromatogram as one of analysis parameters; a data point number storage () configured to store information on an appropriate number of data points corresponding to one peak; a sampling time interval calculator () configured to calculate a sampling time interval, which is a timing for acquiring data for creating the chromatogram, from the inputted peak width and data point number; and an analysis control unit () configured to control an operation of the mass spectrometer so as to acquire ion intensity data in the mass spectrometer according to the sampling time interval.

Chromatograph mass spectrometer

A chromatograph mass spectrometer includes: a chromatograph unit configured to separate components in a sample; a mass spectrometer configured to perform measurement on ions having a specific mass-to-charge ratio derived from each compound temporally separated by the chromatograph unit, an analysis condition setting unit configured to allow a user to set, as an analysis condition, molecular-weight-related information and a mass-spectrometry-related parameter including an ion polarity, a type of an adduct, a number of polymerizations of a multimer and/or an ion valence for each measurement target compound; and an analysis method creator configured to calculate a mass-to-charge ratio of one or a plurality of types of ions according to the analysis condition set by the analysis condition setting unit for the each measurement target compound, and create an analysis method for performing mass spectrometry on the one or a plurality of types of ions in a time division manner.

In a mass spectrometer including ion optical elements for transporting ions or controlling their behavior by electric fields, a device state determiner () determines whether or not the mass spectrometer is in a normal state based on an ion intensity signal acquired by analyzing a predetermined sample. If the mass spectrometer is in an abnormal state, a charge-up determiner () determines whether or not charge-up is present in the ion optical elements based on a change in ion intensity signal in an analysis on the predetermined sample observed when the voltages applied to the ion optical elements are changed according to a predetermined sequence. If charge-up is present, the charge-up determiner determines which ion optical element is likely to have the charge-up. A notifier () notifies a user of the results of the determination by the device state determiner and the charge-up determiner.

Mass spectrometer with charge up determiner using ion intensity signal

Provided is a chromatograph mass spectrometer that includes a component separation unitthat temporally separates components in a sample, a first detectorthat acquires measurement data of components included in an outflowing liquid from the component separation unitby an analysis method different from mass spectrometry, a mass spectrometerthat acquires mass spectrometry data including intensity information for each of mass-to-charge ratios of ions derived from the components contained in the outflowing liquid from the component separation unit, a chromatogram creation unitthat creates a chromatogram representing an intensity change of the measurement data with time based on the measurement data of the first detector, an information extraction unitthat detects a peak based on the intensity change of the mass spectrometry data with time, and extracts information including a representative time of the peak, and a chromatogram display unitthat displays the chromatogram together with additional information corresponding to the extracted time.

A multiport valve used for a water quality analyzer is provided with: a valve head having a plurality of ports for receiving pipings for connections therebetween, the ports being provided on an outer surface of the valve head, the valve head including a connection surface in which ends of flow paths communicating with the respective ports are arranged in the same plane, the valve head being made of a resin material having corrosion resistance against a chemical used in the water quality analyzer; a rotor having a flat surface provided with a groove for switching a connection state between the ends of the flow paths arranged on the connection surface, the flat surface being arranged so as to face the connection surface; and a drive mechanism configured to rotate the rotor.

Multiport valve for water quality analyzer

In a chromatograph mass spectrometer having a measurement unit () including a chromatograph is combined with a tandem mass spectrometry section capable of an MS/MS analysis, a controller () performs chromatograph mass spectrometry by controlling the measurement unit so as to operate the tandem mass spectrometry section to cyclically perform analysis cycles, where each of the analysis cycles includes a first mass spectrometric analysis in which a measurement of ions is performed over a predetermined m/z range and an MS/MS analysis by DIA in which ions included within each of a plurality of windows formed by dividing the m/z range are designated as a precursor ion. A window selector () selects, during an execution of an analysis cycle, a window among the plurality of windows for an MS/MS analysis by DDA which is irregularly performed in an ongoing analysis cycle, based on intensity information obtained for each of the plurality of windows from an MS/MS spectrum acquired by the MS/MS analysis by DIA. A precursor-ion determiner () determines a precursor ion corresponding to the window selected by the window selector in a mass spectrum acquired by the first mass spectrometric analysis in the ongoing analysis cycle, based on peak information included within the m/z range of the window. A data-dependent-acquisition condition setter () informs the controller of the precursor ion determined by the precursor-ion determiner, as the precursor ion for the MS/MS analysis by DDA which is irregularly performed in the ongoing analysis cycle.

The other end of an individual sample supply channel one end of which is connected to a gas buffer container the inside of which is empty is connected to one sub-port of a valve that selects one of standard samples to be supplied to an ESI probe. During analysis, the standard sample stored in one of liquid sample containers is selected by switching a connection state of the valve. The standard sample supplied by being pushed by a gas sent to the liquid sample containers through liquid supply gas branch channels is sent to the ESI probe through a sample supply main channel. At the time of finishing analysis, when the valve is switched such that the sub-port and a main port are communicatively connected, a nitrogen gas is sent to the sample supply main channel, and the remaining liquid is discharged.

Liquid sample introduction method and liquid sample introduction device

When a Q-TOF type mass spectrometer is operated in an MSmode, a controller (), at the time of measurement, controls voltage generators (to) such that only a V voltage (radio-frequency voltage for mass separation) and a direct-current bias voltage are applied to main rod electrodes of a quadrupole mass filter () without application of a U voltage (direct-current voltage for mass separation). During a measurement preparation period between a plurality of measurements to obtain one mass spectrum, the controller () controls a U voltage generator () so as to apply the U voltage to the main rod electrodes of the quadrupole mass filter (). Accordingly, a direct-current electric field is formed between adjacent main rod electrodes around an ion optical axis (C) due to a potential difference, and electric charges accumulated in rod holders () holding the main rod electrodes are rapidly removed by an effect of this electric field. As a result, it is possible to eliminate a charge-up that has not been eliminated by a conventional method in which a polarity of a direct-current bias voltage applied to the rod electrodes is merely reversed.

Mass spectrometer

To acquire a mass spectrum for a wide mass range, a normal analysis execution controlling unit controls components to repeatedly perform measurement while changing setting m/z by a predetermined m/z at a time, and a mass spectrum summarizing processing unit summarizes data pieces each obtained by each time of measurement to generate the mass spectrum. Radio-frequency voltage applied to an ion guide and the like is changed based on the setting m/z. The radio-frequency voltage for the setting m/z is determined using a table in which a relationship between a position on an axis between upper and lower limits of the mass range and the radio-frequency voltage is substantially the same regardless of the mass range.

Time-of-flight mass spectrometer

A liquid sample introduction system for an ion source which ionizes a liquid sample by supplying the liquid sample to an ionization probe in an ion source and blowing an atomization-promoting gas at the liquid sample exiting from the tip of the ionization probe, the system including: a hermetically closable liquid sample container for holding a liquid sample; a liquid-supply-gas passage having one end connected to a point in a passage for an atomization-promoting gas leading to the ion source, and the other end connected to a space above a liquid level in the liquid sample container; a sample supply passage having one end connected to a space below the liquid level in the liquid sample container and the other end connected to the ionization probe; and a passage-switching unit in the sample supply passage for switching the sample supply passage between the communicating state and the closed state.

Liquid sample introduction system for ion source

A liquid sample analyzing system including an ion analyzer having a first ion source receiving a target sample and a second ion source receiving a reference sample; a liquid sample introduction mechanismincluding a passage-switching section introducing reference samples into the second ion source; and a controller for repeatedly performing a series of steps in the ion analyzer, the steps including: a pre-measurement step for initiating a measurement; a measurement step for introducing a target sample into the first ion source and performing a measurement on an ion originating from the target sample along with an ion originating from a reference sample introduced into the second ion source by the liquid sample introduction mechanism; and a post-measurement step where the liquid sample introduction mechanism operates concurrently with the predetermined post-measurement step to switch the passage-switching section to a passage having a reference sample for the next analysis.

Liquid sample analysis system

When there are a plurality of concentration value candidates, an extreme value of the calibration curve is detected, and the number of calibration points respectively contained in a region having a low concentration and a region having a high concentration is calculated using the extreme value as a boundary. If there is a difference between the numbers of calibration points of both regions, a concentration value candidate present in the region having a larger number of calibration points is selected as a quantitation result. When the numbers of calibration points are the same, the sign of the coefficient of the term of the second degree of the calibration curve is assessed, and a concentration value candidate present in a region in which the relationship between peak area values and concentration values is monotonically increasing is selected as a quantitation result.

Growing community of inventors

Kyoto, Japan

Kazuma Maeda